200914132 九、發明說明： 【發明所屬之技術領域】 本發明關於一種烯烴聚合用方法，而且更特別是一種 用於將觸媒粉末飼入烯烴聚合反應器之方法。特別地，本 發明關於一種藉特殊設計之計量轉動閥將觸媒成分（較佳 爲鉻爲主觸媒）分配及引入聚合反應器之方法。 【先前技術】 鉻爲主聚合觸媒，亦稱爲菲利浦觸媒，數十年來已成 功地用於乙烯（共）聚合物之製造。菲利浦觸媒通常藉由 以無機撐體接觸鉻化合物，繼而在35〇至950 t之溫度煅燒 該撐體而製備。氧化鋁、硫酸鋁或矽石可作爲無機撐體， 其可以含鉻溶液（如硝酸鉻（111)或乙酸鉻（111)於水或甲醇 中）浸漬。然後將溶劑蒸發且將經浸漬撐體在氧化條件下 活化’例如在400至1 000°C之含氧大氣中，以產生鉻（VI) 物種：此煅燒步驟將價數小於6之鉻轉化成六價鉻c r (V I) 。因此菲利浦觸媒含大量六價狀態之鉻：不幸地，鉻（V I) 已經證明爲高毒性，而且某些含Cr(VI)廢料被視爲致癌物 。此外在處置含C r (V I)廢料前，其強制將C r ( V I)物種轉化 成較低價之非毒性鉻物種（通常爲三價或二價物種）。 由於以上原因，鉻爲主觸媒粉末必須非常小心地處理 ，特別是在關於將觸媒粉末分配及飼入聚合反應器中之工 業步驟，其目標爲對涉及聚合設施之正常運作及其維護的 全部操作者確保高安全程度。 在此技藝已知用於將適量觸媒粉末分配及輸送至聚合 200914132 反應器之轉動閥的用法。許多不同型式之轉動閥及計量設 備已敘述於專利及文獻中。 美國專利第4,764,056號揭示一種用於將自由流動粉 狀物質以經控制方式在壓力下引入空間中之不連續計量設 備，如聚合反應器。此計量設備包含可交錯地轉動180。之 軸，其具有兩個位於相反側且在面對觸媒貯器單元之側取 得觸媒粉末，及在轉動後在面對終端單元之側按聚合反應 器壁沖洗而釋放之穴。接收計量之觸媒粉末的終端單元爲 圓柱形穴，噴嘴形朝向反應空間且以密封環與塡函蓋密封 。終端單元包含相對圓柱形穴置中且可產生行程移動之心 軸。其藉該心軸之交錯移動及藉加壓惰氣將對應軸之下降 體積與轉動頻率的觸媒粉末量計量至反應器中。 歐洲專利第1 5 7 5 84號敘述一種用於將催化活性粉末 引入流體化床反應器之裝置及方法。此裝置包含適合將觸 媒粉末飼入計量裝置之儲存附件，計量裝置可循序連接該 儲存附件及配置於流體化床反應器上游之中間室。中間室 係置於計量裝置下方以直接接收後者輸送之粉末。計量裝 置較佳爲在存在於上下游之壓力下不漏氣，而且可將計量 體積之觸媒粉末定期輸送至中間室中。計量裝置爲轉動型 且包含至少一個可交錯地連接儲存附件與中間室之穴，此 穴具有截角圓錐形狀，其基底直徑爲其高度之〇.5至1〇倍 之間。 歐洲專利第628 343號敘述一種用於促進反應器之飼 入附件經注射管線將固體引入反應器中之方法。其將固體 -6- 200914132 引入飼入附件中，其中大部分在靜止時沉降，及連 氣體正切地引入該飼入附件之壁以懸浮固體形成由 送之固體的懸浮液至注射管線中。用於將固體引入 件中之轉動閥包含可交錯地連接固體儲存最低部分 附件頂部之穴。該轉動閥亦可爲歐洲專利第1 5 7 5 8 4 者。 以上先行技藝文件中揭示之轉動閥包含具有在 作期間將觸媒粉末維持在周圍所需壓力’亦防止觸 擴散至轉動閥外部之功能的密封系統。 在Cr爲主觸媒系統存在下進行烯烴聚合法時， 部設備中必須維持3 0至4 5巴之高壓力値以提供觸 之計量。因此計量閥之密封裝置必須保證閥內部之 値。然而閥之密封環因轉子之定期轉動及其相對定 擦而磨損及消耗，使得密封效率隨時間而降低，及 之粒狀粉末可通過密封環，如此擴散至閥外部之自 中。此情況在鉻爲主觸媒粉末之情形極爲危險，因爲 物種可毒害在聚合設施中作業之操作者。 其主要希望在將鉻爲主觸媒飼入聚合反應器時 可拾取最終通過密封環之觸媒粉末的裝置之轉動閥 轉移觸媒粉末不與操作者作有害之接觸。 【發明內容】 因此本發明之第一目的爲一種用於將觸媒粉末 合反應器之方法，其包含： a)藉包含定子、轉子、及排列於該定子與該轉子間 續地將 氣體輸 飼入附 與飼入 號所述 分配操 媒粉末 其在全 媒粉末 該壓力 子之摩 極少量 由大氣 Cr(VI) 利用具 ，如此 引入聚 之密封 -7- 200914132 裝置的轉動閥將觸媒粉末計量； b)將經計量觸媒粉末自該轉動閥轉移至聚合反應器； 此方法進一步包含以下步驟： Ο將沖洗化合物飼入一或多個排列在該轉動閥之轉子中的 內導管； d)將觸媒粉末自該密封裝置沖除。 本發明之方法可成功地開發將觸媒粉末引入以氣相及 液相操作之聚合反應器中。藉所述轉動閥可準確地及可靠 地將觸媒（如鉻爲主聚合觸媒）之可能危險性粉末計量至 聚合反應器中，而對設施操作者之健康無任何風險。 然而本發明之方法亦可開發計量多種高活性聚合觸媒 ’本發明不限於使用菲利浦觸媒。適合用於烯烴聚合法之 所有已知聚合觸媒均可考量，唯一應滿足之要求爲將觸媒 以粉末形式飼入。該觸媒較佳爲以自撐形式使用，例如在 撐體材料上’如無機氧化物（例如氧化鎂或矽石）、氯化 鎂、乙氧鎂。 觸媒粉末亦可爲含屬於元素週期表第IV、V或VI族 之過渡金屬（如鈦、釩、锆、或給）的觸媒。其可特別地 爲含上述過渡元素於鹵化形式之戚-納型觸媒。較佳爲戚-納固體成分包含支撐於氯化鎂上之四氯化鈦化合物。 固體成分亦可爲包含至少兩種不同聚合觸媒之混成觸 媒’第一成分爲週期表第4-6族金屬之單環戊二烯基錯合 物爲主聚合觸媒，第二成分爲具有三牙配位子之鐵成分爲 主聚合觸媒。 200914132 觸媒粉末較佳爲支撐在耐火氧化物（如矽石）上之氧 化鉻爲主且藉熱處理活化之菲利浦觸媒。這些觸媒包括化 學地固定在矽膠上之三氧化鉻（VI)。這些觸媒係在氧化條 件下藉由將已摻雜鉻（III)鹽（先質或前觸媒）之矽膠加熱 而製造。在熱處理期間，鉻（III)氧化成鉻（VI)，將鉻（VI) 固定且排除羥基成爲水。 依照本發明之轉動閥的特定設計可達成最終通過閥之 密封裝置的觸媒粉末之連續去除。特別地，在轉動閥內部 流動之沖洗惰性化合物拾取粉末且將其輸送至置於轉動閥 外部之收集系統。粉末可由該收集系統容易地轉移至連續 處理步驟，在此藉由將Cr( VI)物種還原成較低價之非毒性 鉻物種（通常爲三價或二價物種）而使鉻系觸媒無害。 依照本發明，在轉動閥內部流動之沖洗化合物可爲對 觸媒粉末爲惰性之任何化合物。其可以氣態或液態飼入轉 動閥。沖洗化合物無論如何，沖洗化合物較佳爲選擇較常 用於烯烴聚合反應器之惰性化合物，即氮與C2-C8烷屬烴 。沖洗化合物較佳爲選自氮、丙烷、異戊烷、己烷、環己 烷。 飼入沖洗化合物以帶走觸媒粉末可有效地長時間利用 轉動閥而無需定期分解閥本身：其表示相對計量轉動閥之 先行技藝具體實施例的大優點，其中自密封裝置漏出之鉻 觸媒定期地需要將轉動閥完全分解以準確地清潔其內部零 件。依照本發明之具體實施例，轉動閥之內部零件可長時 間保持清潔而無需定期分解閥。 200914132 在依照本發明之方法中’上述步驟b)及d)爲同時操作 。此外以上定義步驟〇及步驟d)較佳爲以連續方式操作。 轉動閥之結構性排列包含轉子、定子、及排列於該轉 子與該定子間之密封裝置。閥之轉子包含： -一或多個用於收集及將觸媒粉末計量之凹部； -一或多個沿其軸向方向排列之內導管，該內導管連接位 於閥之密封裝置附近之室。 依觸媒型式而定，離開轉動閥之經計量觸媒粉末可視 情況地在連續飼入聚合反應器之前轉移至觸媒活化步驟。 在步驟b)中’其藉氣態或液態載體將經計量觸媒粉末 連續地轉移至聚合反應器。在轉移菲利浦觸媒時，該載體 較佳爲氮或氣態丙烷，而在將戚-納觸媒轉移至聚合反應器 時其較佳爲丙烷。 【實施方式】 第1圖顯示藉依照本發明之轉動閥將鉻爲主觸媒計量 ’其可沖除最終通過密封裝置之觸媒粉末。 轉動閥包含實質上圓柱形之轉子1(其可圍繞其軸轉 動）、包圍該轉子1之定子2、包含一序列包夾在該轉子1 與該定子2間之密封環4的密封裝置3，作爲組成元件。 定子2之上部包含可接收來自觸媒儲存槽（如觸媒桶 或觸媒加料漏斗）之固態觸媒的第一通道5。同樣地，定 子2之底部包含可將經計量觸媒粉末輸送至下游設備（例 如觸媒活化容器或聚合反應器）之第二通道6。 在第1圖之具體實施例中，轉子1具有相對轉子軸對 -10- 200914132 稱地排列之二凹部7a與7b。轉子1按確立頻率轉動180° 之角度，使得凹部7a與7b相互地對應通道5或通道6而 安置：結果在將凹部7a充塡來自通道5之觸媒粉末時，另 一凹部7b由於粉末因重力掉落至通道6中而清空。 按時間單位經計量及轉移之觸媒粉末量係依凹部7a 與7b之大小、尤其是轉子1之轉動頻率而定。 密封裝置3包含雙列密封環4隔離外部周圍與存在於 閥內部之操作條件。在第1圖中，相對凹部7a與7b密封 環4a、4b、4c係排列於左側，而密封環4d、4e、4f係排 列於右側。 密封環4a、4b、4c、4d、4e、4f各爲充塡PTFE (聚 四氟乙嫌）之低摩擦露波環（lubroring)。 轉動閥亦包含在閥之一側上間隔轉子1與定子2之軸 承8a與8b，及在閥之另一側上間隔轉子1與定子2之密 封軸承9a與9b。 轉子1進一步具有二內導管10a與l〇b，其係沿轉子 軸向方向定向且行進通過轉子1之長度，如第1圖所示。 由於在將聚合觸媒粉末計量時存.在於通道5、6及凹部 7a、7b之約25-45巴的高壓力値，亦由於影響密封環4之 高磨損程度（定子1經常轉動，結果摩擦定子2)，極少量 之鉻觸媒可超越密封環4及到達第1圖所示之環形室丨丨與 12 ° 依照本發明之方法’沖洗惰性化合物係沿轉子1之內 導管10a與l〇b飼入’該內導管10a與i〇b連接位於密封 -11- 200914132 環4附近之室n與1 2。結果最終存在於環形室n與i 2 之觸媒粉末被沖洗化合物流拾取且自環形室1 1與丨2沖除 〇 該沖洗化合物之入口點可對應軸承8 a或軸承8 b而安 置：軸承8a與8b未密封，如此可連續飼入沖洗化合物旦 滲透至環形室11。將沖洗化合物拾取之觸媒粉末自環形室 11去除且沿內導管10a與10b輸送。內導管10a與l〇b之 出口會合至環形室1 2中，在此沖洗惰性化合物拾取額外之 觸媒粉末（如果其中存在）。 軸承9a與9b均具有密封裝置，使得強迫帶有粉末之 沖洗化合物進入轉子1內部之通道1 3 a、1 3 b，及連續地流 經出口通道14。拾取之觸媒粉末經出口通道14離開轉動 閥且可在使其無害之處理步驟前轉移至收集槽。 第2圖顯示第1圖沿垂直轉子軸之A A’段的轉動閥。 轉子1在定子2之外殼內部轉動’而且藉凹部7a與7b操 作觸媒粉末之計量及轉移。通道5接收來自觸媒儲存槽之 觸媒粉末，而通道6將經計量觸媒粉末輸送至下游設備。 如第2圖所強調’內導管l〇a、10b較佳爲在轉子1 中依照相對凹部7 a與7 b之對稱位置排列。 第3圖顯示一個其中藉第1-2圖之轉動閥將鉻觸媒粉 末計量及引入氣相聚合反應器的具體實施例。 依照第3圖’其首先藉本發明之轉動閥將化學地固定 在矽膠上之由三氧化鉻（VI)組成的固態觸媒成分計量，然 後轉移及引入乙烯聚合用流體床反應器中。 -12- 200914132 該觸媒成分係以粉末形式在惰性大氣下儲存於觸媒加 料漏斗21內部··粉末之平均直徑可爲5微米至250微米之 範® °觸媒可在惰性大氣下以實質上無液體之乾燥粉末形 式儲存。 加料漏斗21中之壓力較佳爲調整成範圍爲30至45 巴之高値，其較聚合反應器中存在之壓力高約15-30巴之 範圍’以由於壓力梯度而利於將觸媒粉末轉移至反應器中 ’但不必沿觸媒粉末之飼入線路使用任何泵或壓縮機。 依照第3圖之具體實施例，其將鉻觸媒之粉末連續地 飼入聚合反應器30中，而對設施操作者無接觸危險性觸媒 粉末之任何風險。 轉動閥2 2係置於觸媒加料漏斗2 1下方，以直接接收 後者輸送之粉末及操作觸媒粉末之定期體積計量。存在於 閥22之轉子內部的二凹部，如第1-2圖所述，可循序連接 觸媒加料漏斗2 1之底部及轉移線路2 3之入口。 如關於第1圖所述，轉動閥22在通道5、6及凹部7a 、7b包含飼入操作所需之雙列可保持高壓力値的密封環。 將沖洗惰性化合物經線路2 4連續地飼入轉子之內導管中 ，及拾取最終通過密封環之鉻觸媒粉末。然後將富觸媒粉 末之沖洗化合物在轉動閥22外部連續地經線路25移除至 粉末收集槽26。將觸媒粉末自收集槽26經線路27連續地 傳送至製造無害鉻（VI)物種之特殊處理步驟。 轉移線路23連接轉動閥22與用於將觸媒粉¥飼入聚 合反應器之線路28。氣態或液態載體流經控制閥29連續 -13- 200914132 地進入線路2 8 :因而藉該氣態或液態載體將觸媒粉末連 地輸送至流體化床反應器3 0。控制閥2 9具有調整線路 中觸媒載體之流速的功能。觸媒載體係方便地選自較常 於烯烴聚合法之惰性化合物，如氮與C2-C8烷屬烴。在 用鉻爲主觸媒作爲聚合觸媒時，線路2 8之觸媒載體較佳 選自氮或氣態丙院。 乙烯聚合用流體化床反應器30包含生長聚合物顆 用流體化床3 1、流體化格網3 2、及速度降低區3 3。速 降低區3 3通常具有較反應器之流體化床3 1大的直徑。 所述，觸媒粉經線路2 8進入反應器3 0，同時將作爲觸 活化劑之烷基鋁化合物經線路3 4飼入反應器3 0。在藉 利浦觸媒之烯烴聚合的情形，線路3 4之活化劑較佳爲三 銘。 將離開速度降低區3 3頂部之氣流經再循環線路3 5 移至氣/固分離器36，如旋風爐，以自氣態再循環流去除 細微顆粒。將離開分離器3 6頂部之氣流經線路3 7輸送 壓縮機38，然後至熱交換器39。再循環線路37裝有用 飼入乙烯、選用共單體、作爲分子量調節劑之氫、及惰 聚合氣體（如氮或丙烷）的線路40。在製造乙烯共聚物 情形，共單體較佳爲1-丁烯及/或1-己烯。 氣流通過熱交換器3 9而冷卻，然後經分布格網3 2 入流體化床反應器3 0底部。以此方式，向上流動氣體將 合物顆粒床維持在流體化條件。 將製造之聚合物經線路4 1自流體化床3 1下部排放 續 28 用 使 爲 粒 度 如 媒 菲 己 轉 最 至 於 性 之 飼 聚 -14- 200914132 及爲了自排放之聚合物去除大部分之氣體而傳送至固/氣 分離器42。將氣體混合物經線路43飼回再循環線路37， 同時將經脫氣聚合物經線路44送至下游設備，如蒸發、乾 燥及擠壓（未示）。 在第4圖所示之具體實施例中，其將戚-納觸媒成分在 飼入烯烴聚合反應器之前藉本發明之轉動閥52計量。觸媒 成分包含支撐於氯化鎂上之四氯化鈦化合物。 這些觸媒顆粒係在惰性大氣下以粉末形式儲存在觸媒 加料漏斗5 1內部。觸媒可以實質上無液體之乾燥粉末形式 儲存。 轉動閥5 2係置於觸媒加料漏斗5 1下方，以直接接收 後者輸送之粉末及操作觸媒粉末至轉移線路53之定期體 積計量。如關於第1圖所示，將沖洗惰性化合物經線路5 4 連續地飼入轉動閥52之內導管，及拾取最終超越閥之密封 環的觸媒粉末。然後將帶有觸媒粉末之沖洗化合物輸送至 轉動閥5 2外部，然後經管線5 5轉移至粉末收集槽5 6。 轉移線路5 3連接轉動閥5 2與用於將觸媒粉末飼入觸 媒活化容器5 9之線路5 7。氣態或液態載體流經控制閥5 8 連續地進入線路5 7 :因而藉該氣態或液態載體將觸媒粉末 連續地輸送至活化容器5 9。該氣態或液態載體係方便地選 自較常用於烯烴聚合法之惰性化合物，如氮與C2-C8烷屬 烴。在將戚-納觸媒粉末計量時，飼入線路5 7之載體較佳 爲液態丙烷。 將作爲觸媒活化劑之有機鋁化合物（較佳爲三乙鋁） -15- 200914132 經線路60飼入活化容器59。視情況地’電子予體 可經線路6 1飼入活化容器5 9。一旦活化’則觸媒 此自容器5 9抽取且經線路6 2飼入流體化床反應器 流體化床反應器6 3具有用於將固態顆粒在反 部連續再循環之特殊迴圈R:此反應器詳述於本申 國際申請案第PCT/EP2006/06 893 5號。 流體化床反應器63包含聚合物之流體化床64 化格網65、及速度降低區66。速度降低區66通常 反應器之流體化床部分大的直徑。聚合物床係藉經 應器底部之流體化格網6 5飼入之氣體的向上流動 體化狀態。 離開速度降低區66頂部之氣體除了未反應單 包含惰性可冷凝氣體（如烷屬烴）及惰性不可冷凝 如氮）。在氣/固分離器67中將氣體帶有之最細微聚 粒去除。將補充單體、分子量調節劑及選用惰性氣 於壓縮機6 8上游之線路Μ飼入氣體再循環線路。 將再循環氣體混合物藉壓縮機68壓縮，及藉熱 69冷卻。使氣流通過熱交換器69冷卻以散逸反應 後經線路7 0轉移至氣體分布格網7 5下方之流體化 器底部。 流體化床反應器63具有聚合物藉將流體化格雜 接聚合物床64上方之區域的循環迴圈（以代號R表 連續氣力再循環。 將垂直管線71之上端連接流體化格網65，同 化合物 顆粒因 63 ° 應器丙 請人之 、流體 具有較 置於反 保持流 體亦可 氣體（ 合物顆 體經置 交換器 熱，然 床反應 S 65連 示）之 時將其 -16- 200914132 下端連接再循環迴圈R。分布格網65較佳爲以其朝垂直管 線7 1向下傾斜由於重力促成聚合物粉末進入管線7 1中之 方式具有圓錐形。管線7 1之入口較佳爲位於相對流體化格 網6 5之中央位置，如第1圖所示。 將控制閥72裝設在垂直管線7 1附近以調整自反應器 63排放至排放導管73中之聚合物的流速。其可使用分段 球閥或同心轉動型閥作爲控制閥72。聚合物之排放係連續 地進行，而且調整該控制閥72之開口以將流體化床反應器 63內部之固體高度保持固定。將未經排放導管73排放之 聚合物顆粒經循環迴圈R連續地再循環至反應器上區。 「節流氣體」通常在循環迴圈R之入口處經線路74 飼入，該節流氣體爲沿循環迴圈R帶有固態顆粒之氣態載 體。控制閥7 5調整「節流氣體」進入循環迴圈R之流速。 該節流氣體可有利地在壓縮機68下游處，或在熱交換器 69下游處，取自反應器之氣體再循環線路。 將流體化床反應器63中之操作壓力維持在通常爲1〇 至3 0巴間之習知値，溫度爲5 0至1 3 0 °C之間。 本發明之第二個目的爲一種用於將觸媒粉末引入聚合 反應器中之設備，此設備包含： -用於儲存該觸媒粉末之槽或加料漏斗； -計量轉動閥，其包含：定子、轉子、排列於該定子與該 轉子間之密封裝置、及用於將沖洗化合物飼入該閥之轉 子內部的沖洗裝置； -用於將經計量觸媒粉末輸送至該聚合反應器之轉移裝 -17- 200914132 置。 如第1圖所示，轉動閥之沖洗裝置包含按其軸向方向 排列於轉子1中之二內導管l〇a與l〇b。內導管1〇&與l〇b 連接位於密封環4附近之環形室丨〗與1 2。 密封環4包含一列充塡聚四氟乙烯（PTFE)之低摩擦露 波環。 本發明用於飼入觸媒粉末之方法及設備不限於以氣相 進行之聚合方法，而是可成功地應用於烯烴聚合用液相法 ’如溶液聚合。在此情形’在轉動閥內部流動之沖洗化合 物爲對觸媒粉末爲惰性之液態化合物，其較佳爲選自丙院 、異戊烷、環己烷。例如在丙烯之溶液聚合中，沖洗化合 物較佳爲環己烷，其可作爲聚合稀釋劑。 可聚合之α-烯烴具有式CHfCHR，其中R爲氫或具 有1-12個碳原子之烴基團。可得聚合物之實例爲： 高密度聚乙烯（相對密度高於0.940之HDPE)，其包括 乙燦同兀聚合物及具有具3至12個碳原子之稀烴的 乙烯共聚物； - 低密度（相對密度低於〇.94〇之LLDPE )及非常低密度 與超低密度（相對密度低於0.920至0.880之vldpe^ ULDPE)線形聚乙烯，其由具一或多個具有3至12個 碳原子之α -烯烴的乙烯共聚物組成； -乙烯與丙烯及低比例二烯之彈性三聚物、或乙烯與丙嫌 之彈性共聚物（衍生自乙烯之單元的含量爲約3〇至7〇 重量％之間）； -18- 200914132 - 順聯聚丙烯、及丙烯與乙烯及/或其他a -烯烴之結晶共 聚物（衍生自丙烯之單元的含量超過85重量％); - 丙烯與α -烯烴（如1-丁烯）之順聯共聚物（α -烯烴含 量至多3 0重量％ ); - 藉丙烯及丙烯與乙烯之混合物（含至多30重量％之乙烯 )的逐次聚合而得之抗衝擊性丙烯聚合物； - 順聯聚丙烯、及丙烯與乙烯及/或其他α -烯烴之非晶共 聚物（含超過70重量％之衍生自丙烯的單元）。 在用於本發明方法之觸媒粉末包括菲利浦觸媒時，合 適之撐體材料爲無機化合物，特別是多孔性氧化物，如Si 02 、Al2〇3、MgO、Zr〇2、B2〇3、CaO、ZnO，或這些氧化物 之混合物。 撐體材料較佳爲呈現1至3 00微米，特別是30至70 微米間之粒度。特佳撐體之實例爲矽膠、與式Si 02. a A120 3 之鋁矽酸鹽溶膠，其中a表示範圍爲0至2，較佳爲0至 〇·5之數目；因此其爲鋁矽酸鹽或二氧化矽。此產物爲市售 ，例如 G r a c e 之 S i 1 i c a G e 1 3 3 2。 將觸媒撐體摻雜含鉻之活性成分較佳爲由溶液發生， 或者在揮發性化合物之情形爲由氣相發生。合適之鉻化合 物爲氧化鉻（VI)、鉻鹽（如硝酸鉻（III)與乙酸鉻（III))、錯 合物化合物（如乙醯丙酮酸鉻（III)或六羰基鉻）、或鉻之有 機金屬化合物（如貳（環戊二烯基）鉻（II)、有機鉻酯或貳 (芳烴）鉻（0))。其較佳爲使用硝酸鉻（III)。 撐體通常藉由在溶劑中以鉻化合物接觸撐體材料，去 -19- 200914132 除溶劑，及在400至1100°C之溫度煅燒觸媒而裝載。因此 撐體材料可懸浮在溶劑中或鉻化合物之溶液中。 除了含鉻活性成分，其他摻雜物質亦可應用於撐體系 統。合適之此摻雜物質的實例爲硼、氟、鋁、矽、磷、與 鈦之化合物。 這些摻雜物質較佳爲與鉻化合物一起應用於撐體，但 是或可在應用鉻前後之分別步驟中應用於撐體。 在摻雜撐體時適合使用之溶劑的實例爲水、醇、酮、 醚、酯、與烴，甲醇特別適合。 摻雜溶液之濃度通常爲每升溶劑爲0.1至200，較佳 爲1至50克之鉻化合物。 在應用期間鉻化合物對撐體之重量比例通常爲 0.001:1 至 200:1，較佳爲 0.005:1 至 100:1。 依照本發明方法之一個具體實施例’鉻觸媒係藉由對 非活性前觸媒加入少量Mg〇及/或ZnO，繼而以習知方式 將此混合物活化而製備。此手段改良觸媒之靜電性質。 爲了活化，例如在含氧之氧化大氣中，在流體化床反 應器中將乾燥前觸媒在400至11〇〇 °C之溫度煅燒。 爲了防止吸附氧，冷卻較佳爲在惰性大氣下發生。其 亦可在氟化合物（如六氟矽酸銨）存在下進行此煅燒，藉 此將觸媒表面以氟原子修改。 前煅燒階段係在氣相流體化床中發生。依照一個較佳 具體實施例，其首先將混合物藉純惰性氣體（較佳爲氮） 流體化而加熱至200至400°C ’較佳爲2 5 0至3 5 0 °C，繼而 -20- 200914132 以空氣取代，此時將混合物加熱至所需最終溫度。將混合 物在最終溫度保持2至2 0小時且較佳爲5至1 5小時之時 間，然後將氣體流動切換回到惰氣，及將混合物冷卻。 在用於本發明方法之觸媒粉末包括戚-納觸媒成分時 ，以下爲關於此型觸媒系統之進一步資訊。 戚-納觸媒系統包含藉元素週期表（新註）第4至1〇 族之過渡金屬化合物與元素週期表第1、2或13族之有機 金屬化合物的反應而得之觸媒。 ^ 特別地，過渡金屬化合物可選自Ti、V、Zr、Cr、與BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a process for the polymerization of olefins, and more particularly to a process for feeding catalyst powder to an olefin polymerization reactor. In particular, the present invention relates to a method of dispensing and introducing a catalyst component, preferably a chromium-based catalyst, into a polymerization reactor by means of a specially designed metering rotary valve. [Prior Art] Chromium-based polymerization catalyst, also known as Phillips catalyst, has been successfully used in the manufacture of ethylene (co)polymers for decades. The Phillips catalyst is usually prepared by contacting a chromium compound with an inorganic support, followed by calcining the support at a temperature of 35 to 950 Torr. Alumina, aluminum sulfate or vermiculite can be used as the inorganic support, which can be impregnated with a chromium solution such as chromium nitrate (111) or chromium acetate (111) in water or methanol. The solvent is then evaporated and the impregnated support is activated under oxidizing conditions, for example in an oxygen-containing atmosphere at 400 to 1 000 ° C to produce a chromium (VI) species: this calcination step converts chromium having a valence of less than 6 into Hexavalent chromium cr (VI). Therefore, the Phillips catalyst contains a large amount of chromium in the hexavalent state: unfortunately, chromium (V I) has proven to be highly toxic, and some Cr(VI)-containing wastes are considered carcinogens. In addition, it is forced to convert the C r (V I) species into lower-priced non-toxic chromium species (usually trivalent or bivalent species) before disposal of Cr-containing (V I) waste. For the above reasons, chromium-based catalyst powders must be handled with great care, especially in the industrial step of dispensing and feeding the catalyst powder into the polymerization reactor, with the goal of normal operation and maintenance involving the polymerization facility. All operators ensure a high level of safety. The use of a rotary valve for dispensing and delivering a suitable amount of catalyst powder to a polymerization 200914132 reactor is known in the art. Many different types of rotary valves and metering devices are described in the patents and literature. U.S. Patent No. 4,764,056 discloses a discontinuous metering apparatus, such as a polymerization reactor, for introducing a free flowing powdery material into a space under pressure in a controlled manner. This metering device includes a staggerable rotation 180. The shaft has two cavities on the opposite side and takes the catalyst powder on the side facing the catalyst reservoir unit, and is released by the polymerization reactor wall flushing on the side facing the terminal unit after the rotation. The terminal unit that receives the metered catalyst powder is a cylindrical hole that faces the reaction space and is sealed with a sealing ring and a lid. The terminal unit includes a mandrel that is placed in a relatively cylindrical pocket and that produces a stroke movement. By the staggered movement of the mandrel and the pressurized inert gas, the amount of catalyst powder corresponding to the falling volume and the rotational frequency of the shaft is metered into the reactor. European Patent No. 1 5 7 5 84 describes an apparatus and method for introducing a catalytically active powder into a fluidized bed reactor. The apparatus includes a storage accessory adapted to feed the catalyst powder into the metering device, the metering device being sequentially connectable to the storage accessory and to an intermediate chamber disposed upstream of the fluidized bed reactor. The intermediate chamber is placed underneath the metering device to directly receive the powder delivered by the latter. Preferably, the metering device is airtight under the pressures present upstream and downstream, and the metered volume of catalyst powder is periodically delivered to the intermediate chamber. The metering device is of the rotary type and includes at least one pocket that alternately connects the storage attachment to the intermediate chamber, the pocket having a truncated conical shape with a base diameter between 55 and 1〇 of its height. European Patent No. 628 343 describes a method for promoting the introduction of a solid into a reactor via an injection line. It introduces solids -6-200914132 into the feed attachment, most of which settles at rest, and the gas is introduced tangentially into the wall of the feed attachment to suspend solids to form a suspension of solids delivered to the injection line. The rotary valve used to introduce the solids into the insert contains a pocket that can be staggered to the top of the attachment of the lowest portion of the solids storage. The rotary valve can also be the European patent No. 1 5 7 5 8 4 . The rotary valve disclosed in the above prior art document includes a sealing system having a function of maintaining the required pressure of the catalyst powder around during operation and also preventing the diffusion from spreading to the outside of the rotary valve. When the olefin polymerization process is carried out in the presence of Cr as the main catalyst system, a high pressure of 30 to 45 bar must be maintained in the unit to provide the metering. Therefore, the sealing device of the metering valve must ensure the internal pressure of the valve. However, the sealing ring of the valve is worn and consumed by the periodic rotation of the rotor and its relative rubbing, so that the sealing efficiency is lowered with time, and the granular powder can pass through the sealing ring and thus diffuse to the outside of the valve. This situation is extremely dangerous in the case of chromium-based catalyst powders because species can poison operators operating in polymerization facilities. It is mainly desired that the transfer valve of the device which picks up the catalyst powder which finally passes through the seal ring when feeding the chromium-based catalyst into the polymerization reactor does not cause harmful contact with the operator. SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is a method for powder-combining a catalyst, comprising: a) including a stator, a rotor, and a gas disposed between the stator and the rotor; Feeding the distribution medium powder with the feed number described above. In the whole medium powder, the pressure of the pressure is extremely small and is used by the atmospheric Cr(VI). Thus, the rotary valve of the device is introduced into the seal -7-200914132. Powder metering; b) transferring the metered catalyst powder from the rotary valve to the polymerization reactor; the method further comprising the steps of: feeding the rinsing compound into one or more inner conduits arranged in the rotor of the rotary valve; d) The catalyst powder is flushed from the sealing device. The process of the present invention successfully develops a catalyst which introduces catalyst powder into a gas phase and a liquid phase. The rotary valve can accurately and reliably meter the possible hazardous powder of the catalyst (such as chromium-based polymerization catalyst) into the polymerization reactor without any risk to the health of the facility operator. However, the process of the present invention can also be used to develop a variety of highly active polymeric catalysts. The invention is not limited to the use of Phillips catalysts. All known polymerization catalysts suitable for use in the olefin polymerization process can be considered, and the only requirement is to feed the catalyst in powder form. The catalyst is preferably used in a self-supporting form, such as on a support material such as an inorganic oxide (e.g., magnesia or vermiculite), magnesium chloride, or ethoxylated magnesium. The catalyst powder may also be a catalyst containing a transition metal (e.g., titanium, vanadium, zirconium, or nitrile) belonging to Group IV, V or VI of the Periodic Table of the Elements. It may in particular be a ruthenium-nano catalyst containing the above transition element in a halogenated form. Preferably, the bismuth-nano solid component comprises a titanium tetrachloride compound supported on magnesium chloride. The solid component may also be a mixed catalyst comprising at least two different polymerization catalysts. The first component is a monocyclopentadienyl complex of the metals of Groups 4-6 of the periodic table, and the second component is The iron component having a three-dentate ligand is the main polymerization catalyst. 200914132 The catalyst powder is preferably a Phillips catalyst which is mainly supported by chromium oxide supported on a refractory oxide such as vermiculite and activated by heat treatment. These catalysts include chromium trioxide (VI) chemically immobilized on silicone. These catalysts are produced by heating a tantalum rubber which has been doped with a chromium (III) salt (precursor or precatalyst) under an oxidizing condition. During the heat treatment, chromium (III) is oxidized to chromium (VI), chromium (VI) is fixed and the hydroxyl group is removed to water. The particular design of the rotary valve in accordance with the present invention achieves continuous removal of the catalyst powder that ultimately passes through the valve's seal. Specifically, the flushing inert compound flowing inside the rotary valve picks up the powder and delivers it to a collection system placed outside the rotary valve. The powder can be easily transferred from the collection system to a continuous processing step where the chromium-based catalyst is rendered harmless by reducing the Cr(VI) species to a lower-priced non-toxic chromium species (usually a trivalent or bivalent species) . According to the present invention, the rinsing compound flowing inside the rotary valve may be any compound which is inert to the catalyst powder. It can be fed into the rotary valve in a gaseous or liquid state. Rinse Compounds In any event, the rinse compound is preferably selected from the inert compounds commonly used in olefin polymerization reactors, i.e., nitrogen and C2-C8 paraffins. The rinsing compound is preferably selected from the group consisting of nitrogen, propane, isopentane, hexane, and cyclohexane. Feeding the rinsing compound to carry away the catalyst powder effectively utilizes the rotating valve for a long time without the need to periodically decompose the valve itself: it represents a major advantage of the prior art embodiment of the relative metering rotary valve, wherein the chromium catalyst leaking from the sealing device Periodically, the rotary valve needs to be fully disassembled to accurately clean its internal parts. In accordance with a particular embodiment of the present invention, the internal components of the rotary valve can be kept clean for long periods of time without the need for periodic decomposition of the valve. 200914132 In the method according to the invention, the above steps b) and d) are operated simultaneously. Furthermore, the above defined steps and step d) are preferably operated in a continuous manner. The structural arrangement of the rotary valve includes a rotor, a stator, and a seal disposed between the rotor and the stator. The rotor of the valve comprises: - one or more recesses for collecting and metering the catalyst powder; - one or more inner conduits arranged in their axial direction, the inner conduit connecting the chamber adjacent the sealing means of the valve. Depending on the type of catalyst, the metered catalyst powder exiting the rotary valve can optionally be transferred to the catalyst activation step prior to continuous feed to the polymerization reactor. In step b), it continuously transfers the metered catalyst powder to the polymerization reactor by means of a gaseous or liquid carrier. The support is preferably nitrogen or gaseous propane when transferring the Phillips catalyst, and is preferably propane when the ruthenium-nano catalyst is transferred to the polymerization reactor. [Embodiment] Fig. 1 shows that a chromium-based catalyst is metered by a rotary valve according to the present invention, which can flush out the catalyst powder which finally passes through the sealing device. The rotary valve comprises a substantially cylindrical rotor 1 (which is rotatable about its axis), a stator 2 surrounding the rotor 1, and a sealing device 3 comprising a sequence of sealing rings 4 sandwiched between the rotor 1 and the stator 2, As a constituent element. The upper portion of the stator 2 includes a first passage 5 that receives solid state catalyst from a catalyst storage tank such as a catalyst tank or a catalyst addition funnel. Similarly, the bottom of the stator 2 contains a second passage 6 through which the metered catalyst powder can be delivered to a downstream facility, such as a catalyst activation vessel or polymerization reactor. In the specific embodiment of Fig. 1, the rotor 1 has two recesses 7a and 7b which are arranged symmetrically with respect to the rotor shaft pair -10-200914132. The rotor 1 is rotated by an angle of 180° at an established frequency such that the recesses 7a and 7b are disposed corresponding to each other with the passage 5 or the passage 6: as a result, when the recess 7a is filled with the catalyst powder from the passage 5, the other recess 7b is due to the powder Gravity drops into channel 6 and is emptied. The amount of catalyst powder measured and transferred in units of time depends on the size of the recesses 7a and 7b, particularly the rotational frequency of the rotor 1. The sealing device 3 comprises a double row of sealing rings 4 separating the external surroundings from the operating conditions present inside the valve. In Fig. 1, the seal rings 4a, 4b, 4c are arranged on the left side with respect to the recesses 7a and 7b, and the seal rings 4d, 4e, 4f are arranged on the right side. Each of the seal rings 4a, 4b, 4c, 4d, 4e, 4f is a low-friction dew-flush ring filled with PTFE (polytetrafluoroethylene). The rotary valve also includes bearings 8a and 8b which are spaced apart from the rotor 1 and the stator 2 on one side of the valve, and seal bearings 9a and 9b which are spaced apart from the stator 1 and the stator 2 on the other side of the valve. The rotor 1 further has two inner conduits 10a and 10b oriented in the axial direction of the rotor and traveling through the length of the rotor 1, as shown in Fig. 1. Since the high pressure enthalpy of about 25-45 bar of the channels 5, 6 and the recesses 7a, 7b is present when the polymerization catalyst powder is metered, it also affects the high degree of wear of the sealing ring 4 (the stator 1 often rotates, resulting in friction Stator 2), a very small amount of chromium catalyst can be passed over the sealing ring 4 and reach the annular chamber shown in Figure 1 with 12 °. According to the method of the invention, the inert compound is flushed along the inner conduit 10a and 10 of the rotor 1 b Feeding 'The inner conduit 10a and i〇b are connected to chambers n and 12 near the ring 4 of the seal -11-200914132. As a result, the catalyst powder finally present in the annular chambers n and i 2 is picked up by the flushing compound stream and flushed from the annular chambers 1 1 and 2, and the inlet point of the flushing compound can be placed corresponding to the bearing 8 a or the bearing 8 b: bearing 8a and 8b are not sealed so that the continuous feeding of the rinsing compound can penetrate into the annular chamber 11. The catalyst powder picked up by the rinsing compound is removed from the annular chamber 11 and transported along the inner conduits 10a and 10b. The outlets of the inner conduits 10a and 10b are brought into the annular chamber 12 where the inert compound is rinsed to pick up additional catalyst powder if present therein. Both bearings 9a and 9b have sealing means for forcing the flushing compound with powder into the passages 1 3 a, 1 3 b inside the rotor 1 and continuously flowing through the outlet passage 14. The picked catalyst powder exits the rotary valve through the outlet passage 14 and can be transferred to the collection tank before the process step which renders it harmless. Figure 2 shows the rotary valve of Figure 1 along the A A' section of the vertical rotor shaft. The rotor 1 rotates inside the outer casing of the stator 2 and the measurement and transfer of the catalyst powder are performed by the recesses 7a and 7b. Channel 5 receives the catalyst powder from the catalyst storage tank and channel 6 delivers the metered catalyst powder to the downstream equipment. As emphasized in Fig. 2, the inner conduits 10a, 10b are preferably arranged in the rotor 1 in accordance with the symmetrical positions of the recesses 7a and 7b. Figure 3 shows a specific embodiment in which the chromium catalyst powder is metered and introduced into the gas phase polymerization reactor by the rotary valve of Figures 1-2. According to Fig. 3, the solid catalyst component consisting of chromium trioxide (VI), which is chemically fixed to the silicone, is first metered by the rotary valve of the present invention, and then transferred and introduced into a fluidized bed reactor for ethylene polymerization. -12- 200914132 The catalyst component is stored in powder form in an inert atmosphere inside the catalyst addition funnel 21. · The average diameter of the powder can range from 5 microns to 250 microns. The catalyst can be in an inert atmosphere. Store in the form of a dry powder without liquid. The pressure in the addition funnel 21 is preferably adjusted to a high range of from 30 to 45 bar, which is about 15-30 bar higher than the pressure present in the polymerization reactor to facilitate transfer of the catalyst powder to the pressure gradient due to the pressure gradient. In the reactor, it is not necessary to use any pump or compressor along the feed line of the catalyst powder. In accordance with the embodiment of Figure 3, the chromium catalyst powder is continuously fed into the polymerization reactor 30 without any risk to the facility operator being exposed to the hazardous catalyst powder. A rotary valve 22 is placed below the catalyst addition funnel 21 to directly receive the periodic volumetric measurement of the powder delivered by the latter and the operating catalyst powder. The two recesses present inside the rotor of the valve 22, as described in Figures 1-2, are sequentially connected to the bottom of the catalyst addition funnel 21 and the inlet of the transfer line 23. As described with respect to Fig. 1, the rotary valve 22 includes, in the passages 5, 6 and the recesses 7a, 7b, a double row of seal rings that can maintain a high pressure enthalpy for the feeding operation. The rinse inert compound is continuously fed into the inner conduit of the rotor via line 24 and the chromium catalyst powder that ultimately passes through the seal ring is picked up. The rinsing compound of the rich catalyst powder is then continuously removed via line 25 to the powder collection tank 26 outside of the rotary valve 22. Catalyst powder is continuously transferred from collection tank 26 via line 27 to a special processing step for the manufacture of harmless chromium (VI) species. The transfer line 23 is connected to the rotary valve 22 and a line 28 for feeding the catalyst powder into the polymerization reactor. The gaseous or liquid carrier flows through the control valve 29 continuously -13- 200914132 into the line 2 8 : the catalyst powder is thus conveyed to the fluidized bed reactor 30 by the gaseous or liquid carrier. Control valve 29 has the function of adjusting the flow rate of the catalyst carrier in the line. The catalyst support is conveniently selected from inert compounds which are more conventional than olefin polymerization processes, such as nitrogen and C2-C8 paraffins. When a chromium-based catalyst is used as the polymerization catalyst, the catalyst carrier of the line 28 is preferably selected from nitrogen or gaseous propylene. The fluidized bed reactor 30 for ethylene polymerization comprises a fluidized bed 31 for growing polymer particles, a fluidized grid 3, and a velocity reducing zone 33. The velocity reduction zone 33 typically has a larger diameter than the fluidized bed 31 of the reactor. The catalyst powder enters the reactor 30 via line 28 while the alkyl aluminum compound as a sorbent is fed to the reactor 30 via line 34. In the case of polymerization of olefins by means of a catalyst, the activator of line 34 is preferably three. The gas stream exiting the top of the velocity reduction zone 3 3 is moved via a recycle line 35 to a gas/solids separator 36, such as a cyclone, to remove fine particles from the gaseous recycle stream. The gas leaving the top of the separator 3 6 is sent to the compressor 38 via line 37 and then to the heat exchanger 39. The recirculation line 37 is provided with a line 40 for feeding ethylene, selecting a comonomer, hydrogen as a molecular weight regulator, and an inert polymerization gas such as nitrogen or propane. In the case of producing an ethylene copolymer, the comonomer is preferably 1-butene and/or 1-hexene. The gas stream is cooled by heat exchanger 39 and then passed through a distribution grid 3 2 into the bottom of fluidized bed reactor 30. In this manner, the upward flowing gas hydrate particle bed is maintained under fluidization conditions. The produced polymer is discharged from the lower portion of the fluidized bed 31 via line 4, and is used to remove most of the gas for the self-discharging polymer. It is transferred to the solid/gas separator 42. The gas mixture is fed back to the recycle line 37 via line 43 while the degassed polymer is sent via line 44 to downstream equipment such as evaporation, drying and extrusion (not shown). In the particular embodiment illustrated in Figure 4, the rhodium-nanocatalyst component is metered by the rotary valve 52 of the present invention prior to feeding to the olefin polymerization reactor. The catalyst component comprises a titanium tetrachloride compound supported on magnesium chloride. These catalyst particles are stored in the form of a powder in the form of a powder inside the catalyst addition funnel 51. The catalyst can be stored in the form of a substantially liquid-free dry powder. A rotary valve 52 is placed below the catalyst addition funnel 51 to directly receive the powder delivered by the latter and the periodic volumetric metering of the catalyst powder to the transfer line 53. As shown in Fig. 1, the flushing inert compound is continuously fed through the line 5 4 into the inner conduit of the rotary valve 52, and the catalyst powder of the seal ring of the final overrun valve is picked up. The rinsing compound with catalyst powder is then transferred to the outside of the rotary valve 52 and then transferred via line 55 to the powder collection tank 56. The transfer line 53 is connected to the rotary valve 52 and the line 57 for feeding the catalyst powder into the catalyst activation vessel 59. The gaseous or liquid carrier flows continuously through the control valve 58 into the line 57: the catalyst powder is thus continuously delivered to the activation vessel 59 by the gaseous or liquid carrier. The gaseous or liquid carrier is conveniently selected from inert compounds which are more commonly used in olefin polymerization processes, such as nitrogen and C2-C8 paraffins. The carrier of the feed line 57 is preferably liquid propane when metering the cerium-nano catalyst powder. An organoaluminum compound (preferably triethylaluminum) -15-200914132, which is a catalyst activator, is fed via line 60 to activation vessel 59. Optionally, the 'electronic donor' can be fed into the activation vessel 59 via line 6 1 . Once activated 'the catalyst is extracted from the vessel 59 and fed via line 6 2 into the fluidized bed reactor. The fluidized bed reactor 63 has a special loop R for continuously recycling the solid particles in the opposite direction: this The reactor is described in detail in International Application No. PCT/EP2006/06 893 5 to the present application. The fluidized bed reactor 63 comprises a fluidized bed 64 of polymer, and a velocity reduction zone 66. The velocity reduction zone 66 typically has a large diameter portion of the fluidized bed portion of the reactor. The polymer bed is in an upward flow state of the gas fed by the fluidized grid 65 at the bottom of the reactor. The gas exiting the top of the velocity reduction zone 66 contains an inert condensable gas (e.g., a paraffin) and an inert non-condensable such as nitrogen, except for the unreacted unit. The finest particles with which the gas is carried are removed in the gas/solid separator 67. A supplemental monomer, a molecular weight regulator, and a line selected from the upstream of the compressor 68 are fed to a gas recycle line. The recycle gas mixture is compressed by compressor 68 and cooled by heat 69. The gas stream is cooled by heat exchanger 69 to dissipate the reaction and then transferred via line 70 to the bottom of the fluidizer below gas distribution grid 7.5. The fluidized bed reactor 63 has a circulating loop of polymer in a region above the fluidized bed of the fluidized bed 64 (continuous pneumatic recirculation with the code number R. The upper end of the vertical line 71 is connected to the fluidized grid 65, The same compound particles are 63 °, the fluid is more than the anti-retaining fluid can also be gas (the compound is placed in the exchanger heat, then the bed reaction S 65 is shown) and it is -16- The lower end of the 200914132 is connected to the recirculation loop R. The distribution grid 65 is preferably inclined downwardly toward the vertical line 7 1 due to gravity contributing to the polymer powder entering the line 71. The inlet of the line 71 is preferably preferred. Located at a central location relative to the fluidized grid 65, as shown in Figure 1. A control valve 72 is installed adjacent the vertical line 71 to adjust the flow rate of polymer discharged from the reactor 63 into the discharge conduit 73. It may use a segmented ball valve or a concentric rotary valve as the control valve 72. The discharge of the polymer is continuously performed, and the opening of the control valve 72 is adjusted to maintain the solid height inside the fluidized bed reactor 63 constant. The polymer particles discharged through the discharge conduit 73 are continuously recirculated to the upper region of the reactor via the circulation loop R. The "throttle gas" is usually fed through the line 74 at the inlet of the circulation loop R, which is the edge of the gas The circulating loop R carries a gaseous carrier of solid particles. The control valve 75 adjusts the flow rate of the "throttle gas" into the circulating loop R. The throttling gas may advantageously be downstream of the compressor 68, or in the heat exchanger 69. Downstream, the gas recirculation line from the reactor is maintained. The operating pressure in the fluidized bed reactor 63 is maintained at a conventional temperature of between 1 and 30 bar, at a temperature of 50 to 130 °C. A second object of the present invention is an apparatus for introducing a catalyst powder into a polymerization reactor, the apparatus comprising: - a tank or an addition funnel for storing the catalyst powder; - a metering rotary valve The invention comprises: a stator, a rotor, a sealing device arranged between the stator and the rotor, and a flushing device for feeding the flushing compound into the rotor of the valve; - for conveying the metered catalyst powder to the polymerization reactor Transfer -17- 200914132 As shown in Fig. 1, the flushing device of the rotary valve includes two inner conduits l〇a and lb arranged in the axial direction of the rotor 1. The inner conduit 1〇& and l〇b are connected to the seal ring 4 The adjacent annular chamber 1 and 1 2. The sealing ring 4 comprises a column of low-friction dew wave ring filled with polytetrafluoroethylene (PTFE). The method and apparatus for feeding the catalyst powder of the present invention are not limited to being carried out in the gas phase. The polymerization method can be successfully applied to a liquid phase method such as solution polymerization for olefin polymerization. In this case, the rinsing compound flowing inside the rotary valve is a liquid compound which is inert to the catalyst powder, and is preferably selected. From propylene, isopentane, cyclohexane, for example in solution polymerization of propylene, the rinsing compound is preferably cyclohexane, which acts as a polymerization diluent. The polymerizable α-olefin has the formula CHfCHR wherein R is hydrogen or a hydrocarbon group having 1 to 12 carbon atoms. Examples of polymers obtainable are: high density polyethylene (HDPE having a relative density higher than 0.940) comprising an ethylene bismuth polymer and an ethylene copolymer having a dilute hydrocarbon having 3 to 12 carbon atoms; - low density (LLDPE with a relative density lower than 〇.94〇) and very low density and ultra-low density (vldpe^ ULDPE with a relative density of less than 0.920 to 0.880) linear polyethylene having one or more having 3 to 12 carbons An ethylene copolymer composition of an alpha-olefin of an atom; - an elastomeric terpolymer of ethylene and propylene and a low proportion of diene, or an elastomeric copolymer of ethylene and polypropylene (a unit derived from ethylene is about 3 to 7 〇) Between 5% by weight); -18- 200914132 - cis-linked polypropylene, and crystalline copolymer of propylene with ethylene and/or other a-olefins (content of units derived from propylene exceeds 85% by weight); - propylene and α - a cis-copolymer of an olefin (such as 1-butene) (α-olefin content of up to 30% by weight); - an anti-polymerization of propylene and a mixture of propylene and ethylene (containing up to 30% by weight of ethylene) Impact propylene polymer; - cis-linked polypropylene, and propylene and B An amorphous copolymer of an alkene and/or other alpha-olefin (containing more than 70% by weight of units derived from propylene). When the catalyst powder used in the process of the invention comprises a Phillips catalyst, suitable support materials are inorganic compounds, especially porous oxides such as Si 02 , Al 2 〇 3 , MgO, Zr 〇 2, B 2 〇 3. CaO, ZnO, or a mixture of these oxides. The support material preferably exhibits a particle size between 1 and 300 microns, especially between 30 and 70 microns. An example of a particularly preferred support is silicone, and an aluminosilicate sol of the formula Si 02. a A120 3 wherein a represents a number ranging from 0 to 2, preferably from 0 to 〇·5; Salt or cerium oxide. This product is commercially available, for example, S i 1 i c a G e 1 3 3 2 of G r a c e . The doping of the catalyst support with the chromium-containing active ingredient preferably takes place from solution or, in the case of volatile compounds, from the gas phase. Suitable chromium compounds are chromium (VI) oxide, chromium salts (such as chromium (III) nitrate and chromium (III) acetate), complex compounds (such as chromium (III) acetoacetate or chromium hexacarbonyl), or chromium. An organometallic compound (such as ruthenium (cyclopentadienyl) chromium (II), an organic chromium ester or an anthracene (arene) chromium (0)). It is preferred to use chromium (III) nitrate. The support is usually loaded by contacting the support material with a chromium compound in a solvent, removing the solvent from -19 to 200914132, and calcining the catalyst at a temperature of 400 to 1100 °C. Therefore, the support material can be suspended in a solvent or a solution of a chromium compound. In addition to chromium-containing active ingredients, other dopants can be applied to the support system. Examples of suitable dopant materials are compounds of boron, fluorine, aluminum, cerium, phosphorus, and titanium. These dopants are preferably applied to the support together with the chromium compound, but may be applied to the support in separate steps before and after the application of chromium. Examples of solvents which are suitable for use in doping the support are water, alcohols, ketones, ethers, esters, and hydrocarbons, methanol being particularly suitable. The concentration of the doping solution is usually from 0.1 to 200, preferably from 1 to 50, gram of the chromium compound per liter of the solvent. The weight ratio of the chromium compound to the support during application is usually from 0.001:1 to 200:1, preferably from 0.005:1 to 100:1. A particular embodiment of the method according to the present invention' chromium catalyst is prepared by adding a small amount of Mg and/or ZnO to the non-active procatalyst, followed by activation of the mixture in a conventional manner. This means improves the electrostatic properties of the catalyst. For activation, for example, in an oxygen-containing oxidizing atmosphere, the pre-drying catalyst is calcined at a temperature of 400 to 11 ° C in a fluidized bed reactor. In order to prevent adsorption of oxygen, cooling preferably occurs under an inert atmosphere. This calcination can also be carried out in the presence of a fluorine compound such as ammonium hexafluoroantimonate, whereby the surface of the catalyst is modified with a fluorine atom. The pre-calcination stage occurs in a gas phase fluidized bed. According to a preferred embodiment, the mixture is first fluidized by means of a pure inert gas, preferably nitrogen, to a temperature of from 200 to 400 ° C, preferably from 2,500 to 3,500 ° C, and then -20- 200914132 Replaced by air, at which point the mixture is heated to the desired final temperature. The mixture is maintained at the final temperature for a period of from 2 to 20 hours and preferably from 5 to 15 hours, then the gas flow is switched back to the inert gas and the mixture is cooled. Where the catalyst powder used in the process of the present invention comprises a ruthenium-nanocatalyst component, the following is further information regarding this type of catalyst system. The ruthenium-nanocatalyst system comprises a catalyst obtained by reacting a transition metal compound of Groups 4 to 1 of the Periodic Table of the Elements (new note) with an organometallic compound of Group 1, 2 or 13 of the Periodic Table of the Elements. ^ In particular, the transition metal compound may be selected from the group consisting of Ti, V, Zr, Cr, and
Hf之化合物。較佳化合物爲式Ti(OR)nXy-n，其中n爲0 至y之間；y爲鈦之價數；X爲鹵素，及R爲具有1-10個 碳原子之烴基、或COR基。其中特佳爲具有至少一個Ti-鹵素鍵之鈦化合物，如四鹵化鈦或鹵醇鈦。較佳之指定鈦 化合物爲 TiCl3、TiCl4、Ti(OBu)4、Ti(OBu)Cl3、Ti(OBu)2Cl2 、Ti(OBu)3Cl。 較佳之有機金屬化合物爲有機A1化合物，而且特別是 I A卜烷基化合物。烷基-A1化合物較佳爲選自三烷基鋁化合 物，例如三乙銘、三異丁鋁、三正丁鋁、三正己鋁、三正 辛鋁。亦可使用鹵化烷基鋁' 氫化烷基鋁或倍半氯化烷基 鋁（如AlEhCl與AhEtsCl：)) ’視情況地混合該三烷基鋁化 合物。 特別適合之局產率ZN觸媒爲其中將欽化合物支撐在 鹵化鎂（較佳爲MgCl2 )者。 如果目標爲丙烯或高碳α -烯烴之立體特異性聚合，則 -21- 200914132 在觸媒製備中可加入內電子予體化合物（ID):此化合物通 常選自酯、醚、胺、與酮。特別地，其較佳爲使用屬於1，3-二醚、鈦酸酯、苯甲酸酯、與琥珀酸酯之化合物。 除了存在於固態化合物中之電子予體，使用外電子予 體（ED)加入烷基鋁輔觸媒成分或聚合反應器可得到進一步 之改良。這些外電子予體可選自酯、酮、胺、醯胺、腈、 烷氧基矽烷、與醚。電子予體化合物（ED)可單獨或彼此混 合而使用。較佳爲ED化合物係選自脂族醚、酯與烷氧基 / 矽烷。較佳醚爲C2-C2e脂族醚，而且特別是較佳爲具有3-5 個碳原子之環形醚，如四氫呋喃（THF)、二噁烷。 較佳酯爲CmCu脂族羧酸之烷酯，而且特別是脂族單 羧酸之烷酯，如乙酸乙酯、甲酸甲酯、甲酸乙酯、 乙酸甲酯、乙酸丙酯、乙酸異丙酯、乙酸正丁酯、乙酸異 丁酯。 較佳烷氧基矽烷爲式尺/1^23丨（〇尺3)(：，其中&與13爲0 至2之整數，c爲1至3之整數，及和（a + b + c)爲4; R1' I R2與R3爲具1-18個碳原子之烷基、環烷基或芳基。特佳 爲其中a爲卜b爲l，c爲211與R2至少之一選自具3-10 個碳原子之分支院基、環院基或芳基，及R3爲Cl-ClQ院基 (特別是甲基）之矽化合物。此較佳矽化合物之實例爲甲 基環己基二甲氧基矽烷、二苯基二甲氧基矽烷、甲基第三 丁基二甲氧基矽烷、二環戊基二甲氧基矽烷。此外亦較佳 爲其中a爲0，c爲3，R2爲分支烷基或環烷基，及R3爲 甲基之矽化合物。此較佳矽化合物之實例爲環己基三甲氧 -22- 200914132 基矽烷、第三丁基三甲氧基矽烷與第三己基三甲氧 〇 以下實例進一步描述本發明而非限制其範圍。 實例 實例1 自撐鉻觸媒之製備 使用之撐體爲具有320平方米/克之表面積及 升/克之孔體積的粒狀Si02撐體。此撐體係由例如 以商標名Sylopol 3 3 2市售。 將以上粒狀Si02撐體接觸Cr(N03)39H20於甲 液，及在1小時後在低壓下藉蒸餾去除溶劑。 所得中間產物含0.2重量％之鉻。將該中間產物 流體化床中煅燒。首先將混合物以純氮流體化而 3 0 0 °C，繼而以空氣取代，此時將混合物加熱直到達3 之所需最終溫度。將混合物在最終溫度保持超過1 C 然後將氣體流動切換回到氮及將混合物冷卻。 其得到由平均直徑爲85微米之顆粒組成之觸矣 觸媒粉末之計量及飼入 所得銘觸媒粉末之計量及飼入係藉第3圖所示 實施例進行。 如乾燥粉末在氮大氣下儲存在保持在 之壓力的加料漏斗21中。 如關於第1圖所述，位於閥之轉子1內部的二 與7 b可循序連接加料漏斗2 1底部及轉移線路2 3 = 基矽烷 1_75 毫 Grace 醇之溶 在氣相 加熱至 沿 7 00 °C I小時， I粉末。 之具體 3 5巴 凹部7a :入口， -23- 200914132 使得轉動閥2 2接收來自加料漏斗2丨之觸媒粉末且操作觸 媒粉末之定期體積計量及轉移。 閥22之轉子1每轉動180。可計量及轉移25克之上示 觸媒粉末。同時在轉子之該轉動期間，將1〇〇克作爲本發 明沖洗化合物之氮經線路2 4飼入轉子1之內導管1 〇 a、1 〇 b 。如關於第1圖所解釋’該沖洗化合物拾取最終通過轉動 閥之密封環的絡觸媒粉末。將如此富觸媒粉末之該氮流在 轉動閥2 2外部經線路2 5轉移至粉末收集槽2 6。將觸媒粉 末連續地輸送至目標爲使鉻（VI)物種無害之處理步驟。 藉轉動閥22計量且因重力自凹部7b落下之觸媒沿線 路23流動及進入線路28，其爲觸媒至聚合反應器之飼入 線路。 作爲觸媒載體之第二氮流以1 00公斤/小時之量經控 制閥2 9 (其具有適當地調整氮至飼入線路2 8之流速的功 能）進入飼入線路2 8。因而該涉及氮流之氣力運輸將所需 量之觸媒粉末飼入流體化床反應器30。 氣相聚合 使用第3圖之流體化床反應器30進行聚乙烯之製備。 聚合溫度爲112 °C，壓力爲21巴。 將作爲觸媒活化劑之三己鋁經線路3 4飼入反應器3 0 〇 反應氣體混合物係由以下組成（體積％ )·· 56%之乙稀 、0.2 3 %之1 -己烯、2 %之己烷、4 1 · 7 7 %之氮。 爲了自排放之聚合物去除大部分氣體，其將製造之聚 -24- 200914132 乙烯自流體化床反應器30之下部經線路41排放且送至固/ 氣分離器4 2。然後將經脫氣聚合物經線路4 4送至下游設 備，如蒸發、乾燥及擠壓。 由於在轉動閥之內導管內部流動之沖洗化合物之存在 ，使用依照本發明之轉動閥可將Cr觸媒粉末以對設施操作 者爲高安全程度飼入聚合反應器。 實例2 在流體化床反應器中使用1 -丁烯作爲共單體而進行低 密度線形聚乙烯（LLDPE)之製備。 其使用戚-納觸媒’包含以WO 04/106388號專利，實 例1所述之步驟（依照其使用乙酸乙酯作爲內予體化合物 )製備之駄固態觸媒成分，作爲聚合觸媒。 以上觸媒粉末之計量及飼入係藉第4圖所示之具體實 施例進行。將觸媒粉末如由質量平均直徑爲4 5微米之顆粒 組成之乾燥粉末儲存在加料漏斗51，及保持在壓力爲35 巴之丙烷大氣下。 如關於第1圖所述，位於閥之轉子1內部的二凹部7a 與7b可循序連接加料漏斗51底部及轉移線路53之入口， 使得轉動閥52接收來自加料漏斗51之觸媒粉末且操作觸 媒粉末之定期體積計量及轉移。 閥52之轉子1每轉動18〇。造成計量及轉移15克之上 不觸媒粉末。同時在轉子之該轉動期間，將2〇〇克作爲本 發明沖洗化合物之氮經線路54飼入轉子丨之內導管l〇a、 1 〇b。該沖洗化合物拾取最終通過轉動閥之密封環的觸媒粉 -25- 200914132 末。將如此富觸媒粉末之該氮流在轉動閥5 2外部經線路 55轉移至粉末收集槽56。 藉轉動閥5 2計量且因重力自凹部7 b落下之觸媒沿線 路5 3流動及進入線路5 7，其爲觸媒粉末至觸媒活化容器 5 9之飼入線路。 作爲觸媒載體之第二氮流以1 0公斤/小時之量經控制 閥5 8 (其具有適當地調整飼入線路5 7中丙烷之流速的功 能）連續地進入飼入線路5 7。因而該涉及丙烷流之氣力運 輸將所需量之觸媒粉末引入觸媒活化容器59中。 使用三異丁鋁（TIBAL)與氯化二乙鋁（DEAC)之重量比 例爲7 : 1的混合物作爲觸媒活化劑：將該混合物經線路60 飼入活化容器59。此外將作爲外予體之四氫呋喃經線路61 飼入活化容器5 9。將以上觸媒成分在5 (TC之溫度於丙烷中 預先接觸60分鐘。 在離開活化容器5 9後，將活化觸媒粉末引入流體化床 反應器（第4圖之元件符號6 3 )，以在作爲聚合稀釋劑之 丙烷存在下共聚合乙烯與1-丁烯。其使用氫作爲分子量調 節劑。 乙烯Π -丁烯聚合係在80 °C之溫度及2.5 MPa之壓力進 行。氣態反應混合物之組成物：3 5莫耳％之乙烯、丨6莫耳 %之1 -丁烯、7莫耳％之氫、與42莫耳。/β之丙院。 所得LLDPE共聚物顯示0.920克/立方公分之密度、 0.94克/10分鐘之熔化指數ΜΙΕ。聚合物顆粒之平均直徑爲 約9 9 0微米。 -26- 200914132 由於在轉動閥之內導管內部流動的沖洗化合物之存在 ，使用依照本發明之轉動閥可連續地以對設施操作者爲高 安全程度將戚-納觸媒粉末飼入聚合反應器。 【圖式簡單說明】 本發明在以下參考附圖而更詳細地敘述，其爲本發明 範圍之例證而非限制。 第1圖爲本發明之轉動閥沿平行轉子軸段而取之略示 圖。 (" 第2圖爲本發明之轉動閥沿垂直轉子軸段而取之略示 圖。 第3圖顯示本發明方法之第一具體實施例，其中藉第 1-2圖之轉動閥將鉻爲主觸媒計量及引入氣相聚合反應器 中 〇 第4圖顯示本發明方法之第二具體實施例，其中藉第 1 -2圖之轉動閥將戚-納觸媒粉末計量及引入氣相聚合反應 器中。 i 【主要元件符號說明】 1 轉子 2 定子 3 密封裝置 4 密封環 4 a 密封環 4b 密封環 4 c 密封環 -27- 200914132 \. 4d 密封環 4 e 密封環 4f 密封環 5 第一通道 6 第二通道 7a 凹部 7b 凹部 8 a 軸承 8b 軸承 9 a 密封軸承 9b 密封軸承 10a 內導管 10b 內導管 11 環形室 12 環形室 13a 通道 13b 通道 14 出口通道 2 1 加料漏斗 22 轉動閥 23 轉移線路 24 線路 25 線路 26 粉末收集槽 -28 線路 線路 控制閥 流體化床反應器 流體化床 流體化格網 速度降低區 線路 線路 氣/固分離器 線路 壓縮機 熱交換器 線路 固/氣分離器 線路 線路 加料漏斗 轉動閥 轉移線路 線路 線路 粉末收集槽 線路 -29- 200914132 5 8 控制閥 59 觸媒活化容器 60 線路 6 1 線路 62 線路 63 流體化床反應器 64 流體化床 65 流體化格網 66 速度降低區 67 氣/固分離器 68 壓縮機 69 熱交換器 70 線路 7 1 管線 72 控制閥 73 排放導管 74 線路 75 控制閥 Μ 線路 R 特殊迴圈 -30-Compound of Hf. Preferred compounds are of the formula Ti(OR)nXy-n wherein n is between 0 and y; y is the valence of titanium; X is a halogen, and R is a hydrocarbyl group having from 1 to 10 carbon atoms, or a COR group. Among them, a titanium compound having at least one Ti-halogen bond such as titanium tetrahalide or titanium halooxide is particularly preferred. Preferably, the titanium compound is TiCl3, TiCl4, Ti(OBu)4, Ti(OBu)Cl3, Ti(OBu)2Cl2, Ti(OBu)3Cl. Preferred organometallic compounds are organic A1 compounds, and especially I A alkyl compounds. The alkyl-A1 compound is preferably selected from the group consisting of trialkyl aluminum compounds such as triacetin, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexane aluminum, and tri-n-octane aluminum. The trialkylaluminum compound may also be optionally mixed using an alkylaluminum halide 'hydrogenated alkylaluminum or an alkylaluminum sesquichloride such as AlEhCl and AhEtsCl:). A particularly suitable local yield ZN catalyst is one in which the compound is supported on a magnesium halide (preferably MgCl2). If the target is a stereospecific polymerization of propylene or a high carbon alpha-olefin, then-21-200914132 may incorporate an internal electron donor compound (ID) in the preparation of the catalyst: this compound is typically selected from esters, ethers, amines, and ketones. . In particular, it is preferred to use a compound belonging to 1,3-diether, titanate, benzoate, and succinate. In addition to the electron donor present in the solid compound, further modification can be obtained by using an external electron donor (ED) to add an alkylaluminum auxiliary catalyst component or a polymerization reactor. These external electron donors may be selected from the group consisting of esters, ketones, amines, decylamines, nitriles, alkoxy decanes, and ethers. The electron donor compound (ED) can be used singly or in combination with each other. Preferably, the ED compound is selected from the group consisting of aliphatic ethers, esters and alkoxy groups/decane. The preferred ether is a C2-C2e aliphatic ether, and particularly preferably a cyclic ether having 3-5 carbon atoms such as tetrahydrofuran (THF) or dioxane. Preferred esters are alkyl esters of CmCu aliphatic carboxylic acids, and especially alkyl esters of aliphatic monocarboxylic acids, such as ethyl acetate, methyl formate, ethyl formate, methyl acetate, propyl acetate, isopropyl acetate. , n-butyl acetate, isobutyl acetate. Preferably, the alkoxy decane is a ruler / 1 ^ 23 丨 (〇 3) (: where & and 13 is an integer from 0 to 2, c is an integer from 1 to 3, and (a + b + c And R 3 ' I R 2 and R 3 are an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group or an aryl group. Particularly preferably, wherein a is b and l is at least one of c is at least one selected from the group consisting of 211 and R 2 is selected from the group consisting of a compound having 3 to 10 carbon atoms, a ring-based or aryl group, and R3 being a Cl-ClQ-based (especially methyl) anthracene compound. An example of such a preferred anthracene compound is methylcyclohexyl Methoxy decane, diphenyl dimethoxy decane, methyl tert-butyl dimethoxy decane, dicyclopentyl dimethoxy decane. Further preferably, wherein a is 0 and c is 3, R2 is a branched alkyl or cycloalkyl group, and R3 is a methyl group ruthenium compound. Examples of preferred ruthenium compounds are cyclohexyltrimethoxy-22-200914132 decane, tert-butyltrimethoxynonane and third hexyl The following examples further describe the invention without limiting its scope.Examples Example 1 Preparation of self-supporting chromium catalyst The support used was a granular SiO 2 support having a surface area of 320 m 2 /g and a pore volume of liter / gram. This support system is commercially available, for example, under the trade name Sylopol 3 3 2. The above granular SiO 2 support is contacted with Cr(N03)39H20 in a liquid solution, and after 1 hour, the solvent is removed by distillation under reduced pressure. The obtained intermediate product contains 0.2. Chromium by weight. The intermediate product is calcined in a fluidized bed. The mixture is first fluidized with pure nitrogen at 300 ° C, followed by air, at which point the mixture is heated until the desired final temperature of 3 is reached. Maintaining a temperature of more than 1 C at the final temperature and then switching the gas flow back to nitrogen and cooling the mixture. This results in the measurement of the contact catalyst powder consisting of particles having an average diameter of 85 microns and the metering of the inductive catalyst powder. Feeding is carried out by the example shown in Figure 3. If the dry powder is stored under nitrogen atmosphere in the addition funnel 21 maintained at pressure, as described in Figure 1, the two and seven are located inside the rotor 1 of the valve. b can be connected sequentially to the addition funnel 2 1 bottom and transfer line 2 3 = decane 1_75 mM Grace alcohol dissolved in the gas phase heated to 7 00 °C h, I powder. Specific 3 5 bar recess 7a: inlet, -23 - 2009141 32 causes the rotary valve 22 to receive the catalyst powder from the addition funnel 2 and periodically meter and transfer the operational catalyst powder. Each time the rotor 1 of the valve 22 is rotated 180, 25 grams of the upper catalyst powder can be metered and transferred. During this rotation of the rotor, 1 gram of nitrogen as the rinsing compound of the present invention is fed into the inner conduit 1 〇a, 1 〇b of the rotor 1 via line 2 4 . As explained in relation to Fig. 1 , the rinsing compound is picked up Finally, the catalyst powder of the sealing ring of the valve is rotated. The nitrogen stream of such a rich catalyst powder is transferred to the powder collecting tank 26 via the line 25 outside the rotary valve 2 2 . The catalyst powder is continuously delivered to the target to treat the chromium (VI) species harmless. The catalyst metered by the rotary valve 22 and dropped by gravity from the recess 7b flows along the line 23 and enters the line 28, which is the feed line for the catalyst to the polymerization reactor. The second nitrogen stream as a catalyst carrier enters the feed line 28 via a control valve 29 (having the ability to properly adjust the flow rate of nitrogen to the feed line 28) in an amount of 100 kg/hr. The pneumatic transport involving the nitrogen stream thus feeds the required amount of catalyst powder to the fluidized bed reactor 30. Gas Phase Polymerization The preparation of polyethylene was carried out using a fluidized bed reactor 30 of Figure 3. The polymerization temperature was 112 ° C and the pressure was 21 bar. The trihexyl aluminum as a catalyst activator is fed into the reactor via line 3 4 . The reaction gas mixture is composed of the following (vol%) · 56% of ethylene, 0.23% of 1-hexene, 2 % hexane, 4 1 · 7 7 % nitrogen. In order to remove most of the gas from the discharged polymer, the produced poly-24-200914132 ethylene is discharged from the lower portion of the fluidized bed reactor 30 via line 41 and sent to the solid/gas separator 42. The degassed polymer is then sent via line 4 to downstream equipment such as evaporation, drying and extrusion. Due to the presence of the flushing compound flowing inside the conduit within the rotary valve, the use of the rotary valve in accordance with the present invention allows the Cr catalyst powder to be fed to the polymerization reactor with a high degree of safety to the facility operator. Example 2 The preparation of low density linear polyethylene (LLDPE) was carried out in a fluidized bed reactor using 1-butene as a comonomer. The use of a ruthenium-nanocatalyst 'includes a ruthenium solid catalyst component prepared by the procedure described in WO 04/106388, the procedure described in Example 1 (using ethyl acetate as an internal donor compound) as a polymerization catalyst. The metering and feeding of the above catalyst powder is carried out by the specific embodiment shown in Fig. 4. The catalyst powder, such as a dry powder consisting of particles having a mass average diameter of 45 μm, was stored in an addition funnel 51 and maintained at a propane atmosphere at a pressure of 35 bar. As described with respect to Fig. 1, the two recesses 7a and 7b located inside the rotor 1 of the valve can sequentially connect the bottom of the addition funnel 51 and the inlet of the transfer line 53, so that the rotary valve 52 receives the catalyst powder from the addition funnel 51 and operates. Regular volumetric measurement and transfer of media powder. The rotor 1 of the valve 52 is rotated by 18 turns. Causes measurement and transfer of 15 grams above no catalyst powder. At the same time, during this rotation of the rotor, 2 grams of nitrogen as the flushing compound of the present invention is fed via line 54 into the inner tubes l〇a, 1 〇b of the rotor. The rinsing compound picks up the catalyst powder that ultimately passes through the sealing ring of the rotating valve -25- 200914132. The nitrogen stream of such a rich catalyst powder is transferred to the powder collecting tank 56 via the line 55 outside the rotary valve 52. The catalyst metered by the rotary valve 52 and dropped from the recess 7 b by gravity flows along the line 53 and enters the line 5 7 , which is the feed line of the catalyst powder to the catalyst activation container 59. The second nitrogen stream as a catalyst carrier continuously enters the feed line 57 via a control valve 58 (having the function of appropriately adjusting the flow rate of propane in the feed line 57) in an amount of 10 kg/hr. Thus the pneumatic transport involving the propane stream introduces the desired amount of catalyst powder into the catalyst activation vessel 59. A mixture of 3:1 by weight of triisobutylaluminum (TIBAL) and diethylaluminum chloride (DEAC) was used as a catalyst activator: the mixture was fed via line 60 to an activation vessel 59. Further, tetrahydrofuran, which is an external donor, is fed to the activation vessel 59 via line 61. The above catalyst component was previously contacted with propane for 5 minutes at a temperature of TC. After leaving the activation vessel 59, the activated catalyst powder was introduced into the fluidized bed reactor (component symbol 6 3 of Fig. 4) to Ethylene and 1-butene are copolymerized in the presence of propane as a polymerization diluent. Hydrogen is used as a molecular weight regulator. The ethylene-butene polymerization is carried out at a temperature of 80 ° C and a pressure of 2.5 MPa. Composition: 3 5 mol% of ethylene, 丨6 mol% of 1-butene, 7 mol% of hydrogen, and 42 mol. /β of propylene. The obtained LLDPE copolymer showed 0.920 g/cm 3 Density, melting index of 0.94 g/10 min. The average diameter of the polymer particles is about 990 μm. -26- 200914132 Due to the presence of the rinse compound flowing inside the conduit within the rotary valve, the use according to the invention The rotary valve can continuously feed the bismuth-nano catalyst powder into the polymerization reactor with a high degree of safety to the facility operator. [Schematic Description] The present invention is described in more detail below with reference to the accompanying drawings, which is the present invention. Illustrative of scope Fig. 1 is a schematic view of the rotary valve of the present invention taken along a parallel rotor shaft section. (" Fig. 2 is a schematic view of the rotary valve of the present invention taken along a vertical rotor shaft section. A first embodiment of the method of the present invention is shown in which a chromium-based catalyst is metered and introduced into a gas phase polymerization reactor by a rotary valve of Figures 1-2. Figure 4 shows a second embodiment of the method of the present invention. Wherein the bismuth-nano catalyst powder is metered and introduced into the gas phase polymerization reactor by the rotary valve of Fig. 1 - 2. i [Main component symbol description] 1 rotor 2 stator 3 sealing device 4 sealing ring 4 a sealing ring 4b Sealing ring 4 c Sealing ring -27- 200914132 \. 4d Sealing ring 4 e Sealing ring 4f Sealing ring 5 First channel 6 Second channel 7a Recessed part 7b Recessed part 8 a Bearing 8b Bearing 9 a Sealed bearing 9b Sealed bearing 10a Inner tube 10b Inner conduit 11 Annular chamber 12 Annular chamber 13a Channel 13b Channel 14 Outlet channel 2 1 Addition funnel 22 Rotary valve 23 Transfer line 24 Line 25 Line 26 Powder collection tank -28 Line line control valve Fluidized bed counter Fluidized bed fluidized grid speed reduction zone line line gas/solid separator line compressor heat exchanger line solid/gas separator line line feed funnel rotary valve transfer line line line powder collection tank line -29- 200914132 5 8 Control valve 59 Catalyst activation vessel 60 Line 6 1 Line 62 Line 63 Fluidized bed reactor 64 Fluidized bed 65 Fluidized grid 66 Speed reduction zone 67 Gas/solids separator 68 Compressor 69 Heat exchanger 70 Line 7 1 Line 72 Control valve 73 Discharge conduit 74 Line 75 Control valve 线路 Line R Special loop -30-